High-pressure in situ X-ray absorption fine structure measurements for hydrogenation of CO2 to methanol over Zn-doped ZrO2

IF 5.4 3区材料科学 Q2 CHEMISTRY, PHYSICAL

ACS Applied Energy Materials Pub Date : 2024-08-26 DOI:10.1039/d4cy00894d

Shohei Tada , Kazumasa Oshima , Tastuya Joutsuka , Masahiko Nishijima , Ryuji Kikuchi , Tetsuo Honma

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Abstract

Obtaining insights into the active-site structure of a catalyst during high-pressure and high-temperature catalytic reactions is extremely challenging. In this study, changes in the coordination structure of Zn species in Zn-doped ZrO₂ catalysts (Zn/(Zn + Zr) atomic ratio = 9%) during CO₂-to-methanol hydrogenation (cell temperature = 400 °C, pressure = 9 bars) was investigated using high-pressure in situ X-ray absorption fine structure measurements and density functional theory calculations. The formation of Zn–H species, which are considered the active sites for the reaction, was very limited, with most Zn species existing as [ZnO_a] isolated clusters. Additionally, the adsorption of CO₂ at the Zr⁴⁺ sites near the Zn species induced significant distortions in the coordination structure of the Zn species. This study provides new insights into the catalytic active-site structure.

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在掺锌 ZrO2 上进行二氧化碳加氢制甲醇的高压原位 X 射线吸收精细结构测量

要深入了解催化剂在高压和高温催化反应过程中的活性位结构极具挑战性。在本研究中，利用高压原位 X 射线吸收精细结构测量和密度泛函理论计算，研究了 CO2-甲醇加氢（反应池温度 = 400 °C，压力 = 9 bars）过程中掺杂 Zn 的 ZrO2 催化剂（Zn/（Zn + Zr）原子比 = 9%）中 Zn 物种配位结构的变化。被认为是反应活性位点的 Zn-H 物种的形成非常有限，大多数 Zn 物种以 [ZnOa] 孤簇形式存在。此外，在 Zn 物种附近的 Zr4+ 位点吸附 CO2 会导致 Zn 物种的配位结构发生显著畸变。这项研究为催化活性位结构提供了新的见解。

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来源期刊

ACS Applied Energy Materials Materials Science-Materials Chemistry

CiteScore

10.30

自引率

6.20%

发文量

1368

期刊介绍： ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.